This invention relates to utilizing natural gas as a fundamental component for the production of higher order hydrocarbons, and, in particular, to a unique conversion scheme using nitrous oxide as an agent for joining methane groups contained in natural gas to produce such hydrocarbons.
Natural gas is an abundant fossil fuel resource. Recent estimates place worldwide natural gas reserves at about 35.times.10.sup.14 standard cubic feet, corresponding to the energy equivalent of about 637 billion barrels of oil.
A major source of methane is natural gas. Primary sources for natural gas are the porous reservoirs generally associated with crude oil reserves. From these sources come most of the natural gas used for heating purposes. Quantities of natural gas are also known to be present in coal deposits and are by-products of crude oil refinery processes and bacterial decomposition of organic matter. Natural gas obtained from these sources is generally utilized as a fuel at the site.
The composition of natural gas at the wellhead varies but the major hydrocarbon present is methane. For example the methane content of natural gas may vary within the range of from about 40 to 95 vol. %. Other constituents of natural gas may include ethane, propane, butanes, pentane (and heavier hydrocarbons), hydrogen sulfide, carbon dioxide, helium and nitrogen.
Natural gas is classified as dry or wet depending upon the amount of condensable hydrocarbons contained in it. Condensable hydrocarbons generally comprise C.sub.3 + hydrocarbons although some ethane may be included. Gas conditioning is required to alter the composition of wellhead gas, processing facilities usually being located in or near the production fields. Conventional processing of wellhead natural gas yields processed natural gas containing at least a major amount of methane.
A significant portion of the known natural gas reserves is associated with fields found in remote, difficultly accessible regions. Many of these distant sources are not amenable to transport by pipeline. For example, sources that are located in areas requiring economically unfeasible pipeline networks or in areas requiring transport across large bodies of water are not amenable to transport by pipeline. This problem has been addressed in several ways. One such solution has been to build a production facility at the site of the natural gas deposit to manufacture one specific product. This approach is limited as the natural gas can be used only for one product, preempting other feasible uses. Another approach has been to liquefy the natural gas and transport the liquid natural gas in specially designed tanker ships. Natural gas can be reduced to 1/600th of the volume occupied in the gaseous state by such processing, and with proper procedures, safely stored or transported. These processes, which involve liquefying natural gas at a temperature of about -162.degree. C., transporting the gas, and revaporizing it, are complex and energy intensive.
Still another approach has been the conversion of natural gas to higher order hydrocarbons that can be easily handled and transported. The term "higher order hydrocarbon" refers to a hydrocarbon having at least two carbon atoms. In this way easily transportable commodities may be derived directly from natural gas at the wellhead. The conversion of natural gas to higher order hydrocarbons, especially ethane and ethylene, retains the material's versatility for use as precursor materials in chemical processing. Known processes are available for the further conversion of ethane and ethylene to other useful materials.
U.S. Pat. No. 4,199,533 discloses a process for converting methane to higher molecular weight hydrocarbons by using chlorine gas as a recyclable catalyst. The process produces ethylene as a major product along with hydrogen chloride, which is converted to chlorine for recycle in the system. Major drawbacks of the '533 process are the large amount of chlorine required, the necessity of regenerating chlorine from hydrogen chloride to maintain an economically viable system, and the need to use operating temperatures in excess of 1000.degree. C. to produce ethylene. Additionally, the required chlorine is corrosive under such operating conditions.
Methane may be converted to higher hydrocarbons (e.g., ethane, ethylene and higher homologs) by contacting methane with a reducible metal oxide as a selective oxygen source. As the methane is converted to hydrocarbon products and coproduct water, the active oxygen of the metal oxide is depleted, resulting in a reduced metal oxide. The reduced metal oxide is relatively inactive for the oxidative conversion of methane but active oxygen may be replaced by regeneration of a reducible metal oxide. Such regeneration is accomplished by reoxidation of the reduced metal oxide.
Reducible oxides of several metals have been identified which are capable of converting methane to higher hydrocarbons. Oxides of manganese, tin, indium, germanium, lead, antimony and bismuth are particularly useful. See U.S. Pat. Nos. 4,443,649; 4,444,984; 4,443,648; 4,443,645; 4,443,647; 4,443,644; and 4,443,646. Also see U.S. Pat. Nos. 4,499,323 and 4,499,324.
U.S. Pat. No. 4,499,322 and U.S. Pat. No. 4,495,374 disclose and claim a process for the conversion of methane to higher hydrocarbon which comprises contacting methane with an oxidative synthesizing agent containing a promoting amount of alkali metal and/or compounds thereof.
Hinsen and Baerns report studies of a continuous mode for the oxidative coupling of methane wherein regenerating air is cofed with the methane feed. Hinsen, W. and Baerns, M., "Oxidative Koppling von Methan zu C.sub.2 -Kohlenwasserstoffen in Gegenwart unterschiedlicher Katalysatoren", Chemiker-Zeitung, Vol. 107, No. 718, pp. 223-226 (1983). Using a catalyst based on lead oxide and gamma-alumina in a fixed bed reactor operated at 1 atmosphere total pressure and 600.degree.-750.degree. C., they report results of approximately 53% selectivity to ethane and ethylene at 8% methane conversion for a feed consisting of about 50% methane, 25% air and 25% nitrogen. Other metal oxides studies by Hinsen and Baerns included oxides of Bi, Sb, Sn and Mn.
Commonly-assigned U.S. patent application Ser. No. 600,656, filed Apr. 16, 1984, discloses and claims a process for converting methane to higher hydrocarbons by contacting methane and an oxygen-containing gas with a solid which includes a reducible metal oxide and an alkali/alkaline earth metal promoter.
Commonly-assigned U.S. patent application Ser. No. 600,670, filed Apr. 16, 1984, discloses and claims a process for converting methane to higher hydrocarbons by contacting methane and an oxygen-containing gas with a manganese silicate.
Oxidative condensation of methane in the presence of solid superacid catalysts is disclosed in U.S. Pat. Nos. 4,433,192; 4,465,893; and 4,467,130. European Published Patent Application 93,543 discloses a process for aromatizing methane wherein a methane feedstock and an oxidizing agent other than molecular oxygen are contacted at temperatures of about 10.degree. to 600.degree. C. with a solid acidic catalyst having Bronsted acid sites.
Oxidative conversion of methane to higher hydrocarbons by contacting a mixture of methane and a gaseous oxidant with a catalyst contact solid which does not contain a reducible metal oxide in the presence of a chalcogen promoter is disclosed in U.S. Pat. No. 4,879,427.
Despite these advances in the art of oxidative conversion of methane to higher hydrocarbons, a disadvantage has been the general decline in activity and selectivity achieved with various contact agents over time. The reaction products of such processes include a significant amount of carbon oxides, coke and water. Thus, these processes are not adequately selective for higher hydrocarbons. It would be beneficial to increase methane conversions and increase selectivities to the desired hydrocarbon products.
Selectivity for higher order hydrocarbons can be improved by contacting a gas comprising methane with oxides of nitrogen. U.S. Pat. No. 5,406,017 discloses such a reaction in the presence of a nonacidic solid catalyst at a temperature within the range of about 700.degree. to 1200.degree. C. However, the use of oxides of nitrogen may make the process economically unfeasible.
There are at least two conventional commercial methods for the production of nitrous oxide. By one method, nitrous oxide is produced catalytically from ammonia and air using pelletized Mn and Bi oxides as catalysts, reportedly with an 85 percent conversion of ammonia per single pass at 310-350.degree. C. This method is disclosed in a Japanese technical publication entitled "SYNTHESIS OF NITROUS OXIDE BY OXIDATION OF AMMONIA", by T. Suwa, A. Matsushima, Y. Suziki and Y. Namina in Kohyo Kagaku Zasshi, Vol. 64, pp. 1879-1888, 1961 and also in Czech. Patent CS 186,313, issued Nov. 30, 1973 to J. Mikoda, see Chemical Abstract 95(22); 189,494a. The feed gas composition used in this patent was calculated to contain about 2 percent ammonia in 98 percent air and the exit gas concentration of nitrous oxide was about 1 percent. On this basis, the nitrous oxide produced must be separated from a much larger volume of air, resulting in relatively high separation costs. In addition, this catalytic method for producing nitrous oxide from ammonia produces several by-product nitrogen compounds such as nitric oxide and nitrogen dioxide which necessitate additional separation steps.
The second conventional commercial method for the production of nitrous oxide involves the thermal decomposition of ammonium nitrate at about 170.degree. C. according to the equation below: EQU NH.sub.4 NO.sub.3 .fwdarw.N.sub.2 O+2H.sub.2 O
This method is described in Kirk-Othmer's Encyclopedia of Chemical Technology, Volume 2, p.527, (1978). Since ammonium nitrate is considered to be a high explosive, precautions must be taken to minimize the risk of explosion when using this production method, including feeding a concentrated aqueous solution of ammonium nitrate into a reactor at 275.degree. C. However, any dry, molten ammonium nitrate in the system that becomes heated above 250.degree. C. poses a detonation risk according to the equation: EQU NH.sub.4 NO.sub.3 .fwdarw.N.sub.2 +1/2O.sub.2 +2H.sub.2 O
Besides the above two commercial methods for making nitrous oxide, various laboratory methods have also been disclosed. For example, molten nitrate salts have been reported to react with ammonium chloride to produce nitrous oxide, chloride ion, and water according to the equation below: EQU NH.sub.4 Cl+NO.sub.3.sup.- .fwdarw.Cl.sup.- +2H.sub.2 O +N.sub.2 O
Such a reaction is reported in a technical publication by H. Fouzanfar and D. H. Kerridge in J. Inorg. Nucl. Chem., Volume 40, pp. 1327-1330. This reaction leaves a chloride ion residue in the melt and, with extensive reaction over time, the chloride can build up and actually convert the nitrate melt into a chloride melt. Moreover, the presence of chloride ion can lead to well-known corrosion problems with stainless steels and other conventional materials of reactor construction.
U.S. Pat. No. 4,720,377 discloses a method for producing nitrous oxide by a reaction of ammonia with at least one molten nitrate salt of an alkaline earth metal at reaction conditions to produce nitrous oxide. However, this process is not conducted with high activity.
On the basis of the above, an inexpensive safe method for producing nitrous oxide with high activity would be highly desirable.
The present invention overcomes difficulties presently encountered in the art by providing a method by which to convert natural gas to higher order hydrocarbons with high activity and selectivity.